Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to decay resis-tant sheet
material and more particularly to such materials adapted
for use in shoe construction.
2. Description of the Prior Art
For purposes of economy, it has been the practice to
employ syntheti.c sheet material in the manufacture of shoes.
Such "shoeboard" as it has come to be known, comprises a
disposition of an elastomeric binder and particularly a
neoprene or styrene-butadiene elastomer in a fibrous matrix
and is currently in fairly extensive use in counters and
shoe insoles. For durability, especially where the shoeboard
is employed in tropical climates 9 the board must be treated
with a substance which provides the board with resistance to
decay by fungus and other microbial organisms, a property
not naturally possessed by leather and other shoe construction
constituents unless treated chemically.
Metallic quinolinolates, particularly copper-
quinolinolate effectively render some cellulosic materialsresistant to fungus and bacteria However, due to environ-
mental and economic considerations they have not been
successfully employed as a preservative or fungicide in
shoeboard due to difficulty in processing and retention
within the shoe materials over an extended period of time.
~ In addition, it has been found that metallic quinolinolates
; degrade the flexural property oE the shoeboard over time
when used in combination with neoprene or styrene-butadiene
binders.
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Prior art attemps to incorporate the metallic
quinolinolates in a cellulosic sheet have proved less than
satisfactory. For example, incorporation of the powdered
form of the metallic quinolinolate by adding it to the paper
slurry before deposition on the wire has proved ineffective
due to low retention causing an effluent from the papermaking
process which contains unacceptably high levels of metallic
quinolinolates. Further, it is unacceptable to lose these
amounts of metallic quinolinolates since they are expensive
and it is desirable to have effective utilization of the
quinolinolate. Further~ size press application of a
solubilized form of the copper-quinolinolate is also
ineffective due to the leachability of the same by water.
Methods such as those disclosed in U.S. Patent
3,~93,46~ to Bowers et al. and U.S. Patent 3,713,963 to Hager
demonstrate retention rates of approximately 70% of the
theoretical by formation of the metallic quinolinolate in
the pulper by the proper addition of the required compounds
and precipitation thereof, in situ, of the insoluble salt.
However9 methods are also suggested to treat the paper machine
effluent in order to remove the remaining quinolinolate
therefrom 7
Furthermore, it has been observed that the copper-
quinolinolate, bein~ incompatible with the other popular
insole binders namely, neoprene and styrene-butadiene rubber
causes the coagulation of such binders, théreby severely
adversely affe~ting the uniform saturation of the web with
the binder along with the strength and resilience thereof.
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Accordinglyy it is an object of the present
invention to provide a fungus and mold res:istant synthetic
sheet material which overcomes the deficiencies associated
with the prior art.
It is another object of the present invention to
provide a fungus and mold resistant sheet material employing
a metallic quinolinolate as a funyicide.
It is another object of the present invention to
provide a fungus and mold resistant sheet material of optimal
strength and resilience.
It is another object of the present invention to
provide a method of economically making a fungus and mold
resistant sheet material with a fungicide which is retained
by the sheet material at substantially maximum rates during
the fabrication process. It is another object of the present
invention to provide a fungus and mold resistant material
which retains the fungicide therein over long periods of time.
It is another object of the present invention to
provide a method of making fungus and mold resistant material
~O wherein substantially none of metallic ions from a fungicide
in the material are lost in the effluent or waste water.
These and other objects will become more readily
apparent from the following summary of the invention and
detailed description thereof.
SUMMARY OF T~IE I~VENTIO~
A fungus and mold resistant sheet material is
manufactured from a furnish containing a fibrous pulp, an
ionic emulsion of a metallic quinolinolate as a fungicide
and a cationic polymer for optimization of the retention
of the metallic quinolinolate. The furnish further includes a
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polymer colloid compatible with both the metallic
quinolinolate and an acrylic elastomeric binder added
in a subsequent step' the polymer colloid serves to
prevent the metallic quinolinolate from causing the
coagulation of the binder. The furnish is -then formed
into a web which is sa-turated with the binder, dried
and calendered. The sheet material retains its
flexural properties upon aging.
According to a broad aspect of the present
invention there is provided in a synthetic sheet material
resistant to decay by fungus and other microbial orga-
nisms and which includes a uniform distribution of fibers
and metal-quinolinolate within a binder, the improvement
wherein the binder is an acrylic elastomeric binder in
a sufficient amount to retard the flexural degradation
of the sheet material upon aging.
Accordin~ to a still further broad aspect
of the present invention there is provided a process
for manufacturing a synthetic fibrous sheet material
which is resistant to decay according to a papermaking
technique including providing a furnish of a fibrous
slurry, metal-quinollnolate and a cationic polymer,
forming the furnish into a web, saturating the web with
an acrylic elastomeric binder, and drying the web to
form a fibrous sheet.
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DETAILED DESCRIPTION_OF_THE INVE~TION
In accordance with the present invention the
decay resistant sheet material is formed generally by
a papermaking process and the resulting sheet may be
subsequently laminated to similar sheets to achleve any
desired thickness, strength and stiffness.
In the manufacture of the sheet material, a
furnish is first formed comprising a fibrous pulp and
a cationic polymer. The fibers employed are primarily
cellulosic fibers such as ordinary kraft cook fibers or
the more highly cooked wood cellulose such as the high
alpha, sulfate types used as nitration grade, as well as
jute, hemp, mercerized kraft and the like. A minor
amount of the fibers may be synthetic such as acrylic,
polyester, polyamide and the like, although such synthe-
tic fibers are not strictly necessary. Preferably, the
synthetic fibers may be used at a level of up to about
5% by weight based on the total weight of the fibrous
constituents.
The cationic polymer is added to the pulp at
a concentration of 0.4 to 2.0, and preferably 0.7 to 0.9
parts by weight based upon 100 parts by weight of the
pulp, depositing on the surfaces of the fibers and
providing association sites for the subsequently added
metallic quinolinolate.
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In the preferred embodiment the cationic polymer is a poly-
electrolyte sol~ under the trade name LU~AX 295 by Rohm & Haas
Company and is added to the pulp as a l.0 to 6O0 percent by
weight aqueous solution. In addition to the cationic poly-
electrolyte hereinbefore specified, cationic polyacrylamide
polymers are also useful as the cationic polymer. ~ne cationic
polymer is provided in order to retain the metallic quino-
linolate within the web during processing and additionally to
retain the metallic quinolinolate within the sheet material
during its use as shoeboard and the like. The use of the
cationic polymer to retain metallic quinolinolates in sheet
material -Eor enhanced decay resistance is disclosed in U.S.
Patent No. 4,337,117 issued June 29, 1982 and filed the sam-
day as this application and entitled "Decay Resistant Material"
of Warren J. Bodendorf and Alphonse Presto.
The metallic quinolinolate emulsion, preferably a
copper-8-quinolinolate is then added in the form of an
emulsion to the pulp solution at a concentration of 5 to 12
parts by weight to lO0 parts by weight~of pulp. The copper-8-
quinolinolate is provided in the form of an anionic emulsion,
and is readily bonded to the cationic polymer at the fiber
surfaces. Such an em~lsion is available from Ventron Corp.
under the name CU~NILATE 2~19-75 containing 37.5% weight solids,
7.5/O of which comprises copper-8-quinolinolate.
After the addition of the metallic quinolinolate, the
pH of the mixture is raised approximately to between 8 and ll
and preferably about 8.5 by the addition of a suitable alkali
salt such as sodium aluminate or the like. A polymer colloid
is also added to prevent coagulation of the
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subsequently added saturant binder. The polymer colloid may
be any latex which is compatible with the quinolinolate and
the saturant binder. Preferably, the concentration of the
polymer colloid is S to 12 parts by weight per 100 parts fiberO
In a pre~erred embodimentg the polymer colloid may
comprise ei~her an acrylic latex such as a heat reactive
polyacrylate sold by ~. F. Goodrich Co. under the trade name
XYCAR 2600X112 or a heat reactive polyacrylate sold by
Poly~nerics; Inc. under the trade name of Poly M-410. A dye
may be added with the polymer to achieve any desired color
of the sheet material~
The furnish is then formed into a web by any suitable
apparatus such as, ~or example, a Fourdrinier machine, and
the web is then wet-web saturated with a suitable binder and
prefer~bly an elastomeric ~inder in order to maintain the
integrity of the sheet while enhancing the strength and
resiliency thereofu
The binders useful in the practice of the invention
are those which maintain the integrity of the sheet and do
not degrade the flexural properties of the sheet upon aging~
This retained flexural property is accomplished by the use
of an acrylic elastomeric binder. The term "acrylic
elastomer" as used herein, is meant to encompass polymers
which in their cured state have an extensibility of at least
200% and a memory of at least 90% when stretched within their
extensibility limits and released instantaneously. The
acrylic elastomers useful in the practice of the invention
rnay include small amounts of polymeriæed monomers havlng
con~ugated unsaturation, but necessarily include a major amount
of monoethylenically unsaturated monomers. The monoethyleni-
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cally unsaturated monomers are, but not limited to, the
acrylic monomers such as methacrylic acid, acrylic acid,
acrylonitrile, methacrylonitrile, methalacrylate, methyl-
methacrylate, ethylmethacrylate and the like, monoethyl-
lenically unsaturated hydrocarbons such as ethylene ,
butadiene, propylene, styrene, alpha-methylstyrene and the
like; and other functional unsaturated monomers such as
vinylpyridine, vinylpyrrolidone, acrylamide and the like
functional vinylic monomers. The polymers may be self-
reactive or known crosslinking agents can be added.
When the sheet material is to be used in the
construction of shoes and must exhibit flexibility over its
life time, the acrylic elastomers are necessary because the
flexibility properties of the sheet material fabricated with
the acrylic elastomers do not substantially degrade over time.
A~ter wet-web saturation, the web is calendered to
a suitable gauge and dried. The resulting sheet exhibits a
substantially complete retention of the metallic quinolinolate
and therefore, exhibits an effective long term resistance to
fungus, mold and other microbial organisms. Moreo~er9 the
substantially complete retention of all the metallic quino-
linolates in the web during processing causes the effluent
or process waste water to be substantially free of metallic
ions. Preferably, the metal content due to the quinolinolate
of the total process effluent is below 5 ppm and more
preferably below 2 ppm. Thus specialized pollution abatement
equipment required in the prior art processes to remove
such metals from the process effluent are not required. The
prevention of binder coagulation renders the sheet material
strong and durable and of uniform consistency.
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The following Examples illustrate the typical
preparation of the sheet material of the present invention
and the physical properties associated therewith:
EXAMPLE
Control
A pulper was furnished with 2000 lbs~ of sulfite pulp
and 100 lbso of 1~2 inch 2.2 denier nylon fiber to which
45 gallons of a 4.7% solution of a cationic polymer such as the
hereinbefore described LUFAX 295 were added. 22,5 gallons
(193 lbs.) of the CUNNILATE 2419-75 were added with sufficient
sodium aluminate to raise the pH of the admixture to 8.5.
The furnish was completed by the addition of 45.5 gallons
of a 50% solids styrene-butadiene latex sold under the trade
name ARCO SKD 1084 and 1 lb. 5 oz. of a dye to rid the furnish
of the green tint caused by the copper-8-quinolinolate.
The resulting furnish was then fed to a Fourdrinier
machine forming the furnish into a 48.5 inch wide web.
Following formation, the web was then saturated
with a neoprene latex binder, calendered to 0.129 inch and
dried.
; The sheet material prepared in accordance with
Example I had the following initial properties:
Gau~e ~in.) 0.129
Lbs.~yd. 4.02
Tensil~ (lb) MDl 308
- CD 190
Elongation /O MD 16.25
CD 26.0
_ 9 _
~l6~5
Edge Tear lbs~ MDl 268
CD 198
Taber Stiffness MDl 3150
CD 1300
Elmendorf Tear MDl 4000
(grams~ CD 5050
Internal Bond MDl 3100
(grams) CD2 2200
Mullen (lbs.) 670
Wet Rub 55 x 57
Flex Endurance3 11~198 x 12,375
1. MD = Machine Direction
2. C~ = Cross Direction
3. Flex Endurance according to SATRA physical test method
129M9 1966.
After aging at room temperature for 5 months, the
flexural endurance decreased from 11~198 x 12,375 to 7000 x
4000 and after 1 year decreased to 1 x 1
EXAMPLE II
Example I was repeated except that the neoprene latex
' binder was replaced with an acrylic elastomeric binder sold
under the trade name NACRYLI~ 25-4280 by National Starch &
Chemical Corporation. The NACRYLIC 25-4280 latex is a self
reactive acrylic latex having acrylonitrile polymerized
therein, having a solids~of 51% by weight9 a pH of 2.9, a
viscosity o~ 100 centipoise, and is anionic. Typical film
properties of the latex are such that the film exhibits 600%
elongation, a tensile strengt,h of 350 psi, a second order
glass transition temperature of 4C and a Sward Rocker
Hardness of 0. The ARC0 SKD 1084 was replaced with Polymerics
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410 acrylic resin emulsion. The copper concentration of the
total process effluent was less than 0.50 ppm representing
substantially complete retention of the copper-quinolinolate.
The sheet material prepared in accordance with
Example II had the following initial properties:
Gauge (in.~ .123
Lbs./yd. 3.75
Tensile (lb.) MD 300
CD 190
Elongation % MD 15.5
CD 24.0
Edge Tear lbs. MD 140
CD 129
Taber Stiffness MD 2775
CD 1625
Elmendorf Tear
(grams) MD 3550
CD 4350
Internal Bond
(grams) MD 1700
CD 1450
Mullen lbs n 530
Wet Rub 487 x 733
Flex Endurance 9388 x 5117
EXAMPLE III
Example II was repeated except that the ~auge of the
sheet material was 0.117. The material was subjected to aging
at a temperature of 158F and removed at intervals of seven
days, conditioned for a minimum of 24 hours at 23 + 1C and
50% + 2% relative humidity and tested in the machine direction.
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The test results were as follows:
Oven aging, days 0 7 14 21 28
Tensile, lbs./in 255 260 254 249 241
Elongation, % 14.3 13.0 12.7 13.7 13.7
Stiffness, Taber 2083 2172 2180 2257 2150
Flex, SATRA 3284 3453 2992 2319 2932
The above data demonstrates that the acrylic binder
inhibits, if not alleviates, flexural degradation upon aging
of sheet material containing metal-quinolinolate.
Although the invention has been described by specific
materials and specifid p:rocesses, it is only to be limited so
far as is set forth in the accompanying claims.
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